Mg---NH4 exchange on humic acid: A radiotracer technique for conditional exchange constants in a seawater medium

A radiotracer technique, employing ²⁷Mg, is used to determine the Mg released by ammonium exchange on undis-solved humic acid in a seawater medium. This new method allows for the measurement of exchangeable Mg on the solid phase surface, which eliminates the problem caused by the high-Mg background in the seawater matrix. The precision calculated from the counting statistics is better than ±2%; the reproducibility among repeated counts ranged from ±1% to ±3%. The higher sensitivity of the method allows for monitoring the Mg---NH₄ exchange at concentrations as low as 30 mM NH₄. This is a major improvement relative to the data obtained with the analytical methods used so far, which allow detection of exchangeable Mg only at NH₄ concentrations higher than 1 M. The lower experimental concentrations are more in accordance with the natural ammonium levels found in anoxic marine sediments. For the undissolved humic acid used in this experiment, the amount of exchangeable Mg in apparent equilibrium with an ammonium-free seawater matrix was found to be 96.6 ± 0.4 meq/100g. The Mg---NH₄ exchange on humic acid in seawater comes to a steady-state value in < 18 min. The conditional equilibrium constant obtained for this reaction, K_cond = 0.039 ± 0.001 M⁻¹. The technique can be expanded to other geochemical solid phases in seawater and it can be modified to study the behavior of the major cations by using ²⁴Na, ⁴²K and ⁴⁹Ca.